JPH0228125A - 4-hydroxyphenyl aromatic compound and derivative thereof and production thereof - Google Patents

Abstract

PURPOSE: To advantageously obtain the title compd. by dehydrogenating corresponding tetrakls (4-hydroxyphenyl)cyclohexane or dehydrogenating a condensation product of 1,4-cyclohexadione and phenol without isolating the same.

CONSTITUTION: A compd. represented by formula I [wherein A is a saturated or partially saturated cyclic group generating Ar when H is removed, Ar is 1,4-phenylene, 1,3-phenylene or a polyaromatic group directly bonded or bonded by CO or SO₂, Ph is 1,4-phenylene capable of having 1-2 substituents (1-4C alkyl, halogen or OH), X is OH, SH, OR² or SR² and R² is 1-4C alkyl or benzyl] is dehydrogenated or a compd. represented by formula II (n; 1 or 2) obtained by condensing cyclic mono--di-ketone corresponding to the group A and a compd. represented by formula HPhX is dehydrogenated without being isolated to economically obtain the objective compds. represented by formulae III-TI useful for producing a polymer from the above mentioned raw materials in an industrial scale within one reaction container.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing 4-hydroxyphenyl aromatic compounds, particularly bis(4-hydroxyphenyl) aromatic compounds and derivatives thereof.

4.4'-dihydroxy-p-terphenyl, and related compounds find use in the production of polyethers, polyetherketones, polyethersulfones, polyesters, polycarbonates, and other polymers.

Unsubstituted compounds are particularly useful in making high performance engineering polymers.

According to the first aspect of the present invention, the following formula (I)
[In the above formula, static is 1,4-phenylene, 1,3-phenylene, or directly bonded or C01SO□,0
．． Substituted or unsubstituted aromatic groups selected from polyaromatic groups containing at least two aromatic groups linked by S or CRY (each R independently represents hydrogen, 01-C4 alkyl or fluoroalkyl or phenyl) Ph is 1,4-phenylene optionally substituted with one or two substituents selected from C2-C4 alkyl, halogen or hydroxy; X is OB
, S.R.

OR" or SR"(R" is Cl-C4 alkyl or e.g. methyl or tert-butyl or benzyl)] and its derivatives. The lower formula ■ (in the upper formula,
A is a saturated or partially saturated cyclic group that produces agitation when hydrogen is removed.

"Direct bond" means that the aromatic groups are bonded by a direct bond between the rings, as in biphenylene and cuphenylene, or in a fused ring system, as in naphthalene or pentalene.

If the group Ph is substituted, it is preferably substituted in the 2 or 3 position relative to the group X.

Examples of polyaromatic groups Ar(7) are Ph5OZPh, PhC
0Ph, Ph0Ph.

Ph5Ph, PhCR”ZPh (Each R1 is an independent DH,
CH, or CbHs), and naphthylene (I, 4; 1°5; 2,6; 2,7).

Dehydrogenation is carried out in the presence of a dehydrogenation catalyst.

This is a platinum catalyst, e.g. a platinum supported catalyst (e.g. pi-C
); metallic platinum; palladium catalysts such as platinum oxide, e.g. palladium supported catalysts (e.g. Pd-C, PdBaSO4,
Pd MgO, Pd CaO, Pd AfzO3); metallic palladium; palladium oxide, etc.; rhodium catalysts, such as rhodium composite catalysts (e.g. Rh-C); ruthenium or rhenium catalysts. Pond catalysts include Raney nickel, Raney cobalt, Al or Raney 1, reduced nickel, cobalt or copper; nickel supported, cobalt supported or copper supported catalysts. The use of platinum group metals is preferred if the substrate does not contain reactive groups.

The amount of platinum group metal dehydrogenation catalyst is 0.0 for compound ■
01-0.2 moles of catalyst metal, although other ratios may be used.

Partial dehydrogenation is carried out by thermal decomposition of the compound of formula (1) in the presence of a base, such as Na0II.

Dehydrogenation may be carried out in the presence of an acid or a base, but it is not necessary to use either. Preference is given to using bases such as alkali metal hydroxides such as sulfur hydroxide or potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide or barium hydroxide, carbonates such as sodium carbonate, acetate and phenoxide. . Preference is given to using strong bases, such as sodium hydroxide.

Acid catalysts include Lewis acids such as aluminum chloride, ferrous chloride, and stannous chloride; sulfonic acids such as 4-toluenesulfonic acid and CF35O,H.

Hydrogen acceptors are not required, but may be used. Conventional hydrogen acceptors that may be used include sulfur, selenium, quinones and unsaturated compounds such as alkenes or alkynes. Azo, nitro, carbonyl or phenolic compounds may also be used. Particularly when forming useful compounds, unsaturated compounds are preferred, such as .alpha.-methylstyrene or phenol.

α-Methylstyrene produces cumene, and phenol produces cyclohexanone or cyclohexanol.

The dehydrogenation is preferably carried out at a temperature of 100 to 400°C, more preferably 150 to 300'C.

Preference is given to using a solvent. Conventional dehydrogenation solvents may be used. The overnight reaction is usually carried out under reflux in a relatively high-boiling solvent such as cumene, p-cumene, decalin, nitrohenzene, naphthalene, quinoline or 1-methylnaphthalene. Polyglycol ethers, such as triglyme, offer convenience of removal during finishing and the advantage of a wide range of boiling points due to their compatibility with water. Vigorous boiling or passing an inert gas through the solution is often used to stir the mixture and remove hydrogen from the isolated system. A hydrogen acceptor may be used as a solvent. In a preferred method, the hydrogen acceptor is represented by the following formula (2), HPhX ([), for example phenol, and is used in the condensation reaction to produce the compound of formula (2). Water may be present in this dehydrogenation step.

The formation of triaryl compounds is advantageous in that the dehydrogenation proceeds at lower temperatures than, for example, the formation of biaryl compounds from cyclohexanone and phenol. This is attributed to the formation of a 2fII double bond upon removal of two molecules of HP h X, eg phenol, from the tetrakis compound.

Compound 2) is produced by condensation of compound 2) and a cyclic dione. A convenient method described in US Pat. No. 4,277,600 involves passing hydrogen chloride through a mixture of these reagents.

Suitable diones include cyclohexane-1,4-dione, cyclohexane-1,3-dione, bicyclohexyl-4
, 4'-dione, bicyclohexyl-3,4'-dione, propane-2,2-bis(cyclohexane-4-one), bicyclohexane(3,3,0)-2,5-dione (bentalan) dione), decalin-1,5-dione, decalin-1,4-dione, decalin-2,6-dione,
bis(cyclohexyl)-ketone-4,4'-dione,
and bis(cyclohexyl)sulfone-4,4'-dione. protected or masked Zeon,
For example, tetraacetates or bisketals of these diones may be used.

Substituted diones may also be used. Suitable substituents are R and C
02R (R represents C5-C4 alkyl).

According to the second aspect of the present invention, the following formula (1), (X-Ph), -8r
(IV) (In the above formula, Ar, Ph and A step of forming a compound represented by a cyclic mono- or diketone corresponding to group A and the following formula HPhX
By condensation of the compound represented by (I[[) and dehydrogenation of compound 1, this dehydrogenation is carried out without isolation of compound V.

Cyclic mono- or diketones are introduced in protected or masked form. This is observed when n=2 and compound (2) is the above-mentioned compound (2).

This process has found particular application in the industrial scale production of biphenyl and terphenyl compounds. For example, the compounds disclosed in EP240362 and EP251614 are economically produced by this method. This method allows operation within one reaction vessel, facilitating industrial application of the present invention.

In the condensation step, the compound 1 reactant is preferably present in an excess of, for example 2 to 20, especially 5 to 10 times, the keto groups. It therefore acts as a solvent in both stages and as a hydrogen acceptor in the dehydrogenation stage.

The condensation reaction is preferably acid catalyzed. Suitable acid catalysts include Bronsteso F acids (optionally in the presence of water), such as IIX (X=F, C/2, Br, I), )+2
sO4, H3PO4, halogenated acetic acids, sulfonic acids such as benzenesulfonic acid, triflic acid, polymeric acids such as cation exchange resins containing sulfonic acid groups (such as Amb
erlyst 15, Nafion-H). Lewis acids, such as [lF3, AlC1y, ZnC1z
, or aluminum phenate may be used alone or in combination with the Bronsted heptad acids described above. Zeolites in acid form may be used. For example 1-1 of the total reaction mixture
When water is present at 0% w/w, it is believed that the purity of the product of subsequent dehydrogenation is not affected. In particular, concentrated hydrochloric acid may be used instead of gaseous hydrogen chloride, the water present in the hydrochloric acid and formed by the condensation reaction being subsequently removed in one distillation.

Additionally, promoters containing thiol or thioether groups, such as 11□S, alkylmercaptans, mercapto-amines or thiazoles, may be used with the above acids.

Compound (1) The reactant may be any compound that is not substituted at the 4-position. In preferred compounds,
X is OH. The ketone reactant can be any of the above diones or corresponding monoketones.

For the dehydrogenation step, the solution of compound V containing unreacted compound 1 is made alkaline by addition of a strong base, for example NaOH. A dehydrogenation catalyst, e.g. PdC, is added and the temperature raised to 160-200"C to distill the water. The mixture is then heated at reflux until the dehydrogenation is complete (e.g. 4 hours), then cooled and acidified. After acidification, the product compound (1) is filtered from the resulting mixture, optionally after addition of water to keep unreacted and generated phenol in solution to facilitate filtration at low temperatures.

To form compound (1), a basic catalyst such as Na or phenate may be used. In this case, addition of alkali before dehydrogenation is not necessary.

The invention will be further illustrated by way of example without limiting it.

Tetraphenol, 1,1,4.4-j-trakis(4-hydroxyphenyl)cyclohexane, was prepared according to the method disclosed in Example 1 of FLAME US Pat. No. 4,776,004.

This tetraphenol (mp 316-324°C) is at least 95% pure by 'H and 'C-NMR.
It was shown that

Sodium hydroxide (0,82 g), 5% palladium on charcoal (0,12 g) in a stainless steel autoclave.
), α-methylstyrene (6,60g) and water (3
1,1,4,4-tetrakis(4-hydroxyphenyl)cyclohexane (I3,58g) with 0h+4
was heated at 250°C for 3.5 hours. Further sodium hydroxide (2.0 g) was added and the mixture was poured into glacial acetic acid (50%) while stirring. The solid product was collected, washed with water and dried under vacuum at 50'C.

This 4.4″-dihydroxy-p~terpheni/l/
(7.88 g) was shown to be 95% pure by 1H and C-NMR.') I-NMI?
Spectra are 6.98, 7.63 and 7.73pP
It contained a resonance at II+. ' ``C-IJMR
The spectrum is 115.6.125.9127, L 13
It contained resonances at 0.3.138.0 and 156-9ppI11. Actual measurement C=81.84%, H=5.
51%, calculated C-82, 42%, ) (=5.38%. The melting point of this product was determined in a closed tube and was 378.6
~380.6"C.

1,4-Cyclohexadione (0.40 mol, 44.8 g) and phenol (
6.4 mol, 600 g) was added. This mixture was heated at 50°
C to form a solution and add concentrated hydrochloric acid (sg = 1.18
) (20tall) was added. The mixture was then stirred at 50'C for 7.0 hours.

Add sodium hydroxide (0,75 mol, 30 g) and 5% palladium on carbon (2,0 g) until the bot temperature is 1
Low-boiling substances were removed until a temperature of 80°C was reached (approximately 50 m
1). The mixture was then refluxed for 4 hours at 180-18
5°C), cooled to 50"C and added glacial acetic acid (60°C) and water (100d).

Collect the solid product and incubate until the phenol odor disappears.
Rinse with water at 0°C 3 x 300rn1), under vacuum 1
Dry at 00°C to obtain 36.7g (catalyst (2.0g)
(Yield 35.0% based on 1,4-cyclohexanedione).

The product was converted to N-methylpyrrolidone (NMP) (I75m
1), heated to 150'C, filtered and Pd
/C catalyst was removed. The product was collected and diluted once with NMP (5
0d), washed twice with methanol (50mf) and dried under vacuum at 120'C for 3 hours.

Yield is 24.43g, ip is 378-381°C
Met. The infrared spectrum showed the product of Example 2.

14.4”-dihydroxy--500 fitted with nitrogen inlet, stirrer, thermometer and long air cooler
1,4-cyclohexadione bis(ethylenekecool) ([120 mol, 40.04
g ) and phenol (2,13 mol, 200 g
) was added. The mixture was heated to 70°C to form a solution, cooled to 50°C and concentrated hydrochloric acid (I0ml) was added. The mixture was then stirred at 50'C for 6.0 hours and left at room temperature overnight.

Addition of sodium hydroxide pellets (0.38 mol, 15 g) with stirring followed by 5% palladium (I,
0g) was added. The apparatus was set up for distillation and the reaction mixture was heated until it reached 180°C. The mixture was refluxed for 4 hours and 20 minutes (180°C), cooled to 50'C and glacial acetic acid (30d) followed by water (50ml) was added. After further cooling to room temperature, the solid was collected, washed twice with water, and dried for 100 minutes under vacuum.
It was dried at C.

The product (yield: 110 g) was recrystallized from N-methylpyrrolidone to yield 7.1 with a mp of 378°C.
Obtained 0g. The infrared spectrum showed the product of Example 2.

Claims (1)

[Claims] 1. The following formula I ,SO_2
, O, S or C_R_2 (each R independently hydrogen, C_1
Ph is a substituted or unsubstituted aromatic group selected from polyaromatic groups containing at least two aromatic groups bonded by C_4 alkyl or fluoroalkyl or phenyl; Ph is optionally C_1 to C_4
1,4-phenylene substituted with one or two substituents selected from alkyl, halogen or hydroxy; X is OH, SH, OR^2 or SR^2 (R^
2 is C_1-C_4 alkyl or benzyl] A method for producing bis(4-hydroxyphenyl) aromatic compounds and their derivatives represented by the following formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) A method characterized by comprising a step of dehydrogenating a compound represented by the above formula (wherein A is a saturated or partially saturated cyclic group that yields a group Ar when hydrogen is removed) . 2. The following formula IV, (X-Ph)_n-Ar(IV) [In the above formula, Ar is 1,4-phenylene, 1,3-phenylene, directly bonded, or CO, SO_2
, O, S or CR_2 (each R is independently hydrogen, C_1~
Ph is a substituted or unsubstituted aromatic group selected from polyaromatic groups containing at least two aromatic groups bonded by C_4 alkyl or fluoroalkyl or phenyl, and Ph is optionally C_1 to C_4 alkyl, 1,4-phenylene substituted with one or two substituents selected from halogen or hydroxy; X is OH, SH, OR^2 or SR^2 (R^2
is C_1-C_4 alkyl or benzyl; n is 1 or 2] A method for producing a 4-hydroxyphenyl aromatic compound or a derivative thereof represented by the following formula V, ▲ mathematical formula, chemical formula, There are tables etc.▼(
V) Dehydrogenation of the compound represented by (in the above formula, A is a saturated or partially saturated cyclic group which yields the group Ar when hydrogen is removed) and subsidence with a cyclic mono- or diketone corresponding to the group A. Formula III, HPhX(II
I) formation of a compound V by condensation of a compound of the formula (the dehydrogenation being carried out without isolating the compound V).